Liquid detergent-sanitizer



United States Patent 3,223,644 LIQUID DETERGENT-SANITIZER Andrew B. Law,Levittown, 1221., assignor to Rohm 8: Haas Company, Philadelphia, Pa., acorporation of Delaware No Drawing. Filed Nov. 12, 1964, Ser. No.410,720 9 Claims. (Cl. 252106) This application is acontinuation-in-part of my application Serial No. 146,016 which wasfiled on October 18, 1961, and which has since been abandoned.

This invention relates to a liquid detergent-sanitizer of high hardwater tolerance. It has particular reference to a composition containinga quaternary ammonium composition as the sanitizer and a nonionic as thedetergent.

One of the principal components of the present invention is anoutstanding commercially available sanitizer which consists of anaqueous solution of a mixture of alkyl dimethyl benzyl ammoniumchlorides. The mixture consists of alkyl dimethyl benzyl ammoniumchlorides whose alkyl groups can range from C to C although its mostelfective germicidal components are those whose alkyl groups are C(lauryl or dodecyl), C (myristyl or tetradecyl), and C (cetyl orhexadecyl). The proportions of the C -C components can vary, dependingupon the manufacturer and the particular batch of the product. However,for the purposes of the present invention the proportions are notcritical, the sanitizer being effective in its various proportions, someto a greater and others to a lesser degree, in the invention asdescribed hereinbelow.

One of the most outstanding features of this conventional quaternarysanitizing composition is its exceptional effectiveness in hard water.The sanitizing dilution for quaternaries which is considered standard inthe United States and in most foreign countries is 200 p.p.m., and inmany states and local governments this requirement is specified by law.At this dilution the hard water ceiling for the quaternary mixturedescribed above is 550 p.p.m. hard water. This means that the mixture iscapable of killing 99.999 percent of specified test organisms, in 30seconds, in water containing up to 550 p.p.m. (32 grains per gallon)hardness calculated at CaCO when tested by the method of Chambers (1.Milk & Food Tech, vol. 19, No. 7 (1956), pp. 183-187). This method isalso known as the Association of Official Agricultural Chemists,Official Method of Evaluation of Germicidal and Detergent Sanitizers(cf. Methods of A.O.A.C., 9th ed., 1960, Washington, DC, pp. 70-72). Inaccordance with this procedure an inoculum containing a known number ofbacteria is added to hard water solutions of the aciddetergentsanitizerformulations. Aliquots of the solu- 3,223,644 Patented Dec. 14, 1965tions are then removed at timed intervals and the quaternary inactivatedby diluting 1:10 with a lecithin-Tween 80 solution known commercially asLetheen. Tween is a fatty acid ester of anhydrosorbitols which have beensolubilized by etherifying the free hydroxyl groups with ethylene oxide.Agar pour plates are prepared from the Letheen solutions, incubated at37 C. for 48 hours and counted for surviving bacteria. It should beunderstood that, for some applications, this stringent kill/ timerequirement need not be met. For example, a killing power of 99.999percent in seconds for water of the same hardness may be acceptableunder appropriate circumstances.

With the development of this quaternary it was believed that the needfor a liquid detergent-sanitizer of high hard water tolerance,particularly for use in the dairy and restaurant fields, could easily bemet. However, when the quaternary was combined with any one of a numberof well-known nonionic surfactants that are commonly used indetergent-sanitizer formulations, it was discovered that the hard watertolerance of the quaternary was greatly reduced. The detergentefficiency of the nonionics generally being so high, it became desirableto devise a detergent-sanitizer which would have the detersiveadvantages of the nonionics without appreciably sacrificing the hardwater tolerance of the quaternary.

The present invention exceptionally satisfies the need just described.It consists of a detergent-sanitizer formulation of which the sanitizeris the mixture of alkyl dimethyl benzyl ammonium chlorides definedabove, and the detergent is a mixture of an ethoxylated 11-14 carbonamine having the general structural formula in which 11:1 to 80. Thecarbon values for this amine, it should be understood, are averagevalues. Thus, a C amine is a mixture and may have as its constituentssome compositions that are below as well as some that are above a valueof C but the average will be about C The same applies to each of theother amines in the indicated range.

Optionally, there can be incorporated in the formulation one or morealkaline builders or sequestering agents. Examples of suitable additivesare sodium hydroxide, sodium tripolyphosphate, tetrasodiumpyrophosphate, trisodium phosphate, sodium metasilicate, and the sodiumand potassium salts of ethylenediamine tetraacetic acid.

By way of comparison, Table I shows the results of Chambers tests of thecompatibility of a number of excellent nonionic detergents with the hardwater tolerance of the quaternary mixture. It will be seen that all thecombinations thus tested failed to show the required bactericidal effecteven in water hardness of only 500 p.p.m.

TABLE I [Chambers tests comparing compatibility of several nonionicdetergents with the hard water tolerance of a (Is-C18 alkyl dimethylbenzyl ammonium chloride sanitizer using an AOAC synthetic hard water.]

See footnotes at end of table.

TA-BLE I Continucd Exposure Time in Seconds etergent Non l henox ethanol9.5 ethox rou s T.S./ml TNC TN 0 TNC y p y y g p i 408 000 1 e 8 0 t lhe 0 tha 01 30 ethox rou s T.S.m

c y p n xye n y g p Percent Kill-.. 99T5IZI0i Oct 1 henox ethanol cthoxrou s T.S.m1

yp y yg p) Perc/ent Kill... e g 99. 99. 9935 Oct 1 bone ethanol 16 ethoxrou s T.S. ml

yp Xy yg p) Percent Kill... 99 99 99. 9917 Nonylphenoxyethanol (9-10cthoxy groups) I.S./ml TN 0 TN 0 TN 0 Percent Kill... 99

NOTE.NO. organisms/ml. at O time=109,000,000.

1 Total Survival/m1.

2 TN C=Organisins too numerous to count.

20 TABLE II--'Continued NOTES:

- Exposure Time in Seconds (1) The final concentration of activequaternary was Concentration of sodium 200 p.p.m. Tripolyphosphate (2)The final concentration of active detergent was 15 60 200 p.p.m.

(3) The water hardness was 500 p.p.m. g f gfliii g Even the addition ofan alkaline builder or sequester- 00p p m Kinm 99 99 ing agent whichhelps to raise the hard water ceiling of 1 -9 gg -g g g somecompositions failed to provide the required bac- 800 ppm TNC 161,000 60tericidal effect except when abnormally large, impractical 1 000 m gagg; Kill... 147 33 .8323 90. 9993 amounts were added. This is shown inTable II which 'f 'f 993469 100 100 follows.

TABLE II Norm-No. organisms/m1. at 0 time=96,000,000.

, 1 Total Survival/m1. [Chambers tests in which various amounts ofsodium tripolyphosphate 35 2 TN O=Organisms too numerous to count wereadded to attempt to raise hard water tolerance of a (la-(31 alkyldimethyl benzyl ammonium chloride sanitizer and octylphenoxy- NOTES:ethanol (9-10 ethoxy groups)] (1) The final concentration of activequaternary was Exposure Time in Seconds 200 P-P- aq f i fig ggg 40 (2)The final concentration of active detergent was rpo yp p 15 30 60 200p.p.m. in (A) the first four tests and 400 p.p.m.

in (B) the last five tests. A None T.S./ml. ZTNC TNC 470,000 (3) Thewater hardness was 500 p.p.m.

' Percent Kill-.. 99 99 99.5104 200 p.p.m T.s./m1-. TNC TNO 300, 000 Theuse of several combinations of alkaline builders moppm E?? S fggg and/orsequestering agents likewise failed to raise to Percent K111--. 99 9999. 9921 satisfactory levels the bactericidal elfect and hard water 800ppm ggfiggg 332 8 tolerance of another nonionic detergent-sanitizercombination as shown in Table III which follows.

TAB LE III [Chambers tests in which various alkaline builders andsequestering agents were added to attempt to ra se the hard watertolerance of a 03-018 alkyl dimethyl benzyl ammonium chloride sanitizerand octylphenoxyethanol (1243 ethoxy groups)] Norm-No. organisms/nil. at0 time=1l3,000,000.

1 Total Survival/ml.

2 TNC =Orgam'sms too numerous to count. 8 Versenc=Sodium salt ofethylenediaminetetraacetic acid.

. 6 NOTES: A comparison of the results in the foregoing tables (1) Thefirst test was run Without any detergent with those in Table V clearlyillustrates the unique and (2) The final concentration of activequaternary was remarkable effectiveness of the present invention inwhich a particular type of ethoxylated t-carbinamide is em- 200 p.p.m. 1d th d t t h (3) The final concentration of active detergent was 5 iamme 1st 6 mlxture 200 ppm. resen e y e ormu a (4) The water hardnesswas 600 p.p.m. t-C H NH(CH CH O) H Another series of well known,commercially available, where n is 1 to 80. As shown in Table V, thesesurand highly efiicient surfactants were employed as the defactants arequite compatible with the C C alkyl ditergents in combination with a C-C alkyl dimethyl 10 methyl benzyl ammonium chloride sanitizers.

TABLE V [Chambers tests in which various ethoxylated t-carbinamines(t-Cn-14H2:-z0NHz) were screened for compatibility with (J -C18 alkyldimethyl benzyl ammonium chloride snni tizers regarding the hard watertolerance of the mixture] Exposure Time in Seconds Detergent Nonet-Cn-uHza-wNH(CHzCH2O)H T S t-Cn-uHzg-znNH(CHzCHzO)3H r T S /I11lt-C11-14Hz3-20NH(CH2CH20)5H T S t-Cn-uHza-nNH(CHzCHqO); 5H T S /1Tl1 t-C1-1 H23-a0NH(CHaCHnOhH T S /!1 1 t'Cl1-l4 23-59NH(C 2C 2 )10H T St-Cn-nHza-WNH(CHzCHzO)11,511 T S lIIll t-Cn-uHn-zsNH(CH2CHr0)irH T St-Cu-n n-nNH(CH2CH2O)17.aH T S t-C1 4H23-20NH(CHzCHaOhoH T S/ 1 t- 11-142s-20NH(CH2C zO)zz,uH T S t-Cn-uHza-ztNH(CH2CH2O)a H T 5 [I111t-Cn-uHza-zoNH(CH2CH2O)40H .c T S lml t-Cu-nHz uNH(CHaCHzOmH T.S./ml176, 000 2, s00 30 Percent Killru 99. 8257 99.9972 99.9999

Note-N0. organisms at 0 tlme=101,000,000. 1 Total Survival/m1.TNC=0rganisms too numerous to count.

benzyl ammonium chloride sanitizer. These were the NoTEs: surfactantsrepresented by the formula 49 (1) The final concentration of activequaternary was (2) The final concentration of active detergent was 200p.p.m.

(3) The water hardness was 600 p.p.m.

where n is an average of 5, 15 or 25. As shown in Table IV, thiscombination had a lower hard water tolerance than the quaternary alone,and certainly is an unsatisfactory detergent-sanitizer composition.

TABLE IV [Chambers tests in which various ethoxylated t-carbinamines(t-C1g 24H37 4gN I2) were screened for compatibility with a 0 -01alkyldimethyl benzyl ammonium chloride sanitizer regarding the hardwater tolerance of the mixture] Exposure Time in Seconds Detergent NoneI.S./ml. 146, 000 400 0 Percent Kill 99, 8719 999996 100t-C1s-24H3740NH(CH2CH20)5H T.S./rn1 2 TNC TNC 470, 000 Percent Kill. 9999 99.5877 t-C -zrHy-q NH(CHzCHzO)15H T.S./m1 TNC TNC 66,300 PercentKill 99 99 99. 9418 1;-C gz-1H3740NH(CH2CH2O)25H T.S./IT11 TNC TNC 117,000 Percent Kill 99 99 99. 8974 No'rE,No. organisms/ml, at 0time=l14,000,000. 1 Total Survival/ml. 2 TNC=Organisms too numerous tocount.

Names:

(1) The final concentration of active quaternary was As indicated above,the basic compositions of the pres- 200 p.p.m. ent invention can bemodified by the addition of various (2) The final concentration ofactive detergent was alkaline builders and/or sequestering agents. In nocase 200 p.p.m. is the hard water tolerance lessened, and in most casesit (3) The water hardness was 600 p.p.m. is increased. To illustrate, inTable VI there are listed several formulations of the compositions ofthis invention. Table VII indicates the hard Water ceilings of some ofthose formulations.

Table VIII discloses the effect of various sequestering agents on one ofthose formulations.

TABLE VI.FORMULATIONS MADE IN ACCORDANCE WITH PRESENTt-C11-14H2a-2QNH(CH2CH2O) 'mT-T Distilled water Trisodium phosphate-.Sodium metasilicate- Versene* Sodium $65555;

Sodium salt of ethylenediamine tetraacetic acid.

TABLE VII A. Hard Water Ceilings of Composition No. 1 From Table VIExposure Time in Seconds Final Concentratin Water Hardness of ActiveQuaternary 200 p.p.m 500 p.p.m T.S.lml. 105,300 510 0 Percent Kill---99. 9007 99. 9995 100 200 p.p.m 550 p.p.m T.S. ml 176,000 1,740 0Percent Kill-.. 99.8340 99.9984 100 200p.p.n1 600 p.p.m T.S.lml 530,0008,200 200 Percent Kill--- 99.5000 99.9923 99.9998

N0. organisms/ml. at O time=106,000,000

B. Hard Water Ceilings of Composition No. 2 From Table VI 200 p.p.m 500p.p.m T.S.lml 53,000 260 0 Percent Kill--- 99. 9500 99. 9998 100 200p.p.m 550 p.p.m T.S.Iml 240,000 820 Percent Kill--- 99.7736 99.999299.9999 200 p.p.m 600 p.p.m T.S.Iml 700,000 4,900 150 Percent Kill.--99.3396 99.9954 99.9999

N0. organisms/ml. at 0 time=106,000,000

0. Hard Water Ceilings of Composition N0. 3 From Table VI 200 p.p.m 500p.p.m T.S.lml 41,000 50 0 Percent Kill--- 99.9620 99.9999 100 200 p.p.m550 p.p.m T.S.lml 293,000 460 0 Percent Kill-.. 99. 7287 99. 9996 100200 p.p.m 600 p.p.m T.S./ml 760,000 1,830 0 Percent Kill... 99.296399.9983 100 200 p.p.m 650 p.p.m TS. in TNC 5,200 100 Percent Kill-.- 9999. 9952 99.9999

No. or organisms/ml at 0 time=108,000,000

D. Hard Water Ceilings of Composition No. 4 From Table VI 200 p.p.m 550p.p.m T.S.lml ,00 0 Percent Kill--. 99.9352 99.9999 100 200 p.p.m 600p.p.m.---. T.S. m 130,000 43 0 Percent Kill... 99.8796 99.9996 100 200p.p.m 650 p.p.m T.S./m1 TN 2,340 0 Percent Kill-.. .9978 100 200 p.p.m700 p.p.m T.S.Iml TNC 6,600 40 Percent Kill-.. 99. 9939 99.9999

No. organisms/m1. at 0 time=108,000,000

E. Hard Water Ceilings of Composition No. 5 from Table VI 200 p.p.m 500p.p.m T.S.lml 5 0 0 Percent Kill..- 99.9995 100 100 200 p.p.m 550 p.p.mT.S.lml 2,800 0 0 Percent Kill... 99.9972 100 100 200 p.p.m 600 p.p.mT.S.lml 17,200 30 0 Percent Kill-.. 99.9828 99.9999 100 200 p.p.m 650p.p.m T.S.lml 38,000 570 0 Percent Kill-.. 99.9620 99.9994 100 200 p.p.m700 p.p.m T.S.lml 96, 000 1,880 0 Percent Kill... 99.9040 99. 9981 100200 p.p.m 750 p.p.m T.S.lml 250, 000 5, 100 0 Percent Kill--- 99.750099.9949 100 No. organisms/ml. at 0 t1me=100,000,000

1 Total Survival/ml.

2 TNC=Organisms too numerous to count.

TABLE VIII [Chambers tests demonstrating effect of various sequestrantson the hard water tolerance of composition No. 1 from Table VI] ExposureTime in Seconds Alkali or Sequestrant 'I.S./ml. 410, 000 0 Percent Kill.99. 6095 99.9991 100 None T.S./1nl 2 TNC 6, 50 90 Percent Kill. 90 99.9938 90. 9999 Sodium tripolyphosphate. T.S./ml TNC 5, 2 50 Percent Kill99 99.9950 99.9999 Tetrasodium pyrophos- T.S./ml 880,000 2, 210 0 phate.Percent Kill. 99. 1619 99.9979 100 Trisodium phosphate T.S./ml 350, 0001, 300 0 Percent Kill. 90. 6667 99.9988 100 Versene 'I.S./ml 640, 000 1,580 0 Percent Kill 99. 3905 99. 9985 100 Sodium metasilicate T.S./ml176,000 1, 170 0 Percent Kill. 99. 8324 99.9989 100 Norr;.No. oforganisms/mlat 0 time=105,000,000. 1 Total Survival/ml. 2 TNC: Organismstoo numerous to count. 3 Verseue=Sodium salt of ethylenediaminetctraacetic acid.

NOTES:

(1) The final concentration of active quaternary was 200 ppm.

(2) The final concentration of active alkali or sequestrant was 150 ppm.

(3) The water hardness was 600 ppm.

From the foregoing examples and comparisons it will be apparent that Ihave provided a new and highly useful liquid detergent-sanitizer; thatthe combination of a C C alkyl dimethyl benzyl ammonium chloridesanitizer and a mixture of ethoxylated amines having the formula tC HNH(CH CH ),,H 71:1 to 80 surprisingly results in highly compatibledetergentsanitizers with hard water tolerances substantially as high asthat of the quaternary alone; and that the novel detergent sanitizersare also highly compatible with and benefited by alkali builders orsequestering agents.

It will also be clear that, although the particular types of sanitizerand the particular class of detergents are critical to the successfulperformance of the novel compositions, it is possible to vary thecombinations thereof quite widely. The disclosed specific combinationsthereof, with or without addition of alkali or sequestrants, shouldtherefore be understood to be merely illustrative and the invention isnot limited thereto. If higher detergency is desired, a relative drop inthe quantity of the sanitizer in the composition is necessary as moredetergent is added. This would slow down the speed of reaction, i.e.,the rate of bactericidal action. In turn, this would call for moresequestering agent in order to offset the drop in rate of reaction.Thus, although the nature of the amine detergents that are combined withthe samtizers is critical, the relative ratios of the two is not.Preferably, as shown by the data in Table VI above, a ratio of from 2.5to percent of the detergent to 10 percent of the sanitizer (both on avolume basis), is employed in a solution, the balance of whichessentially is water. This range is extended so that there may, in somecases, be more detergent than the sanitizer present in a proportion ofup to 30% of the former to 10% of the latter. Although the preferredranges of the detergent to sanitizer thus are from 1:4 to 1:1, it shouldbe understood that ranges of from 1:6 to 321 may prove acceptable insome applications. Selecting a use ratio of a given combination ofcomponents thus will depend upon ones own satisfaction level and can bedetermined quite simply by those skilled in the art.

I claim:

1. A liquid detergent-sanitizer solution whose principal activeingredients are present in a total amount ranging from about 12.5% toabout by volume, the ratios of said ingredients ranging from 1 partdetergentz6 parts sanitizer to 1 part sanitizerz3 parts detergent, theremainder of the solution consisting of to 87.5% water, the detergentconsisting of an ethoxylated amine having the general formula t'C 1 H232gNH(CH CH O) H in which 11:1 to 80, the carbon values for the aminerepresenting quantities which are averages coming within the indicatedrange, and the sanitizer consisting of a C -C alkyl dimethyl benzylammonium chloride.

2. A liquid detergent-sanitizer solution whose principal activeingredients, by volume, consist of from 2.5 to 30 percent of anethoxylated amine detergent having the general formula t'C11 14H2329NH(CHZCH O) H in which 11:1 to 80, the carbon value for the aminerepresenting quantities which are averages coming within the indicatedrange, 10 percent of a C C alkyl dimethyl benzyl ammonium chloridesanitizer, and the remainder of the solution consisting of about 60.0%to about 87.5 water. i

3. The composition of claim 1 in which the sanitizer is a mixtureprincipally consisting of a C C and C dimethyl benzyl ammoniumchlorides.

4. The composition of claim 1 in which 0.5% to 7.75% of the water isreplaced by an alkaline builder from the class consisting of sodiumhydroxide, phosphate, silicate, and the sodium and potassium salts ofethylenediamine tetraacetic acid.

5. The composition of claim 4 in which the detergent, sanitizer and atleast one of the alkaline builders are in the following proportions, allfigures being represented as percent by volume: 10 percent of thesanitizer, 2.5 to 20 percent of the detergent, and 0.5 to 7.5 percent ofthe builder.

6. A liquid-detergent-sanitizer composition containing, in percent byvolume, about 10 of a C C alkyl dimethyl benzyl ammonium chloridesanitizer, about 10 of an ethoxylated amine detergent having the generalformula and about of distilled water.

7. A liquid-detergent-sanitizer composition containing, in percent byvolume, about 10 of a C -C alkyl dimethyl benzyl ammonium chloridesanitizer, about 10 of an ethoxylated amine detergent having the generalformula t'C11 H23 29NH(CHzCHzO)15H, about 0f water, about 7.50 trisodiumphosphate, and about 0.25 of an alkaline sequestering agent consistingof a sodium salt of ethylenediaminetetraacetic acid.

8. A liquid-detergent-sanitizer composition containing, in percent byvolume, about 10 of a C C alkyl dimethyl benzyl ammonium chloridesanitizer, about 10 of an ethoxylated amine detergent having the generalformula about 72.25 of distilled water, about 7.50 of sodiummetasilicate, and about 0.25 of an alkaline sequestering agentconsisting of a sodium salt of ethylenediaminetetraacetic acid.

9. A liquid-detergent-sanitizer composition containing, in percent byvolume, about 10 of a mixture of alkyl dimethyl benzyl ammonium chloridesanitizer, about 10 of an ethoxylated amine detergent having the generalformula about 75.25 of distilled water, about 0.5 of an alkalinesequestering agent consisting of a sodium salt of ethylene- 11 12diaminetetraacetic acid, and about 4.0 of sodium hy- OTHER REFERENCESdroxlde- Lesser, Soap and Sanitary Chemicals, Detergent Sanitizers,August 1951, pp. 37-39, 67, 69, and 98. References Cited by the ExaminerSequestrene, publ. of Geigy Industrial Chemicals, 1952,

UNITED STATES PATENTS 5 25: and 1, 2 31 2 li l 2 -1 2 XR JULIUSGREENWALD, Primary Examiner. 2,87 ,2 6 9 9 iey 2 2 O XR 2,950,253 8/1960Kling et a1 252 1s2 ALBERT MEYERS Emmmer- 2,950,255 8/1960 Goff 25215210

1. A LIQUID DETERGENT-SANITIZER SOLUTION WHOSE PRINCIPAL ACTIVEINGREDIENTS ARE PRESENT IN A TOTAL AMOUNT RANGING FROM ABOUT 12.5% TOABOUT 40%, BY VOLUME, THE RATIOS OF SAID INGREDIENTS RANGING FROM 1 PARTDETERGENT:6 PARTS SANITIZER TO 1 PART SANITIZER:3 PARTS DETERGENT, THEREMAINDER OF THE SOLUTION CONSISTING OF 60% TO 87.5% WATER THE DETERGENTCONSISTING OF AN ETHOXYLATED AMINE HAVING THE GENERAL FORMULAT-C11-14H23-29NH(CH2CH2O)NH IN WHICH N=1 TO 80, THE CARBON VALUES FORTHE AMINES REPRESENTING QUANTITIES WHICH ARE AVERAGES COMING WITHIN THEINDICATED RANGE, AND THE SANITIZER CONSISTING OF A C8-C18 ALKYL DIMETHYLBENZYL AMMONIUM CHLORIDE.